Oil compositions containing emulsioninhibiting acetylenic compounds



United States Patent 3,280,035 OIL COMPOSITIONS CONTAINING EMULSION-INHIBITING ACETYLENIC COMPOUNDS Francis J. Bonner, Wilmington, Del.,assiguor to Mobil Oil Corporation, a corporation of New York No Drawing.Filed Apr. 17, 1963, Ser. No. 273,571

' 4 Claims. (Cl. 25252) pounded with various detergents, anti-rustagents, antioxidants and other additives which act as oil emulsifiers inthe presence of water. It is desirable to obtain rapid separation andremoval of any Water dispersed in the lubricating oil and this isusually accomplished by centrifuging and/or settling. Obviously, theformation of oil-water emulsions would interfere with any suchseparation of the water from the oil.

It is one of the objects of the present invention to inhibit theemulsifying tendencies of lubricating oils. It is another object toenhance the demulsibility of additivemodified lubricating oilcompositions. It is a further object to add specific surfactants to thecompounded lubricating oils to depress emulsification thereof in thepresence of water. Other objects will be apparent from the followingdescription in which parts and percentages, where used, are by weight.

According to the present invention, it has now been found thatlubricating oil compositions containing detergent and/or other additiveswhich promote emulsification of the oil with water may have suchemulsifying tendencies reduced by adding to such compositions asurfactant organic compound having an acetylenic linkage, that is, anorganic molecule having a triple bond carbon to carbon linkage (CEC).The compounds contemplated herein are hydroxy-substituted orhalogen-substituted acetylenic hydrocarbons which are oil soluble withinthe effective ranges of amounts prescribed herein and which are normallysolids or liquids at room temperature. These compounds generally containfrom about 5 to about 18 carbon atoms, preferably from 6 to 10 carbonatoms and conform to the general formula:

Where R represents a radical selected from the group consisting ofhydrogen, a hydrocarbyl radical having from 3 to about 8 carbon atoms, ahydroxy-substituted hydrocarbyl radical containing from 3 to about 8carbon atoms annd a chloro-substituted hydrocarbyl radical containingfrom about 3 to about 8 carbon atoms, at least one R being a hydroxyorchloro-substituted hydrocarbyl radical of from 3 to about -8 carbonatoms.

Specific examples of the acetylenic compounds contemplated herein arethe following:

Ethynyl cyclohexanol 3-methyl 1-nonyn-3-0l CEO-H The effectiveness ofthe invention has been demon strated by adding typicalacetylenic'compounds to a lubricating oil composition and testing theresultant mixture for demulsibility, that is, the ability to obtainseparation of water from oil-water mixtures. The test procedure used isthe standard ASTM procedure designated as D1401-56T, in which 40 ml. ofthe oil composition being tested is mixed with 40 ml. of distilled waterand the mixture is stirred for 5 minutes at 130 F. in a graduatedcylinder, after which the resulting emulsion is allowed to stand at roomtemperature so that theemulsion breaks and forms separate layers ofwater, oil and emulsion. The time for the emulsion to be reduced to 3ml. or less is noted as the measure of demulsibility.

EXAMPLE 1 The first series of tests using this standard method werecarried out with a fully formulated turbine circulating heavy oilcomposition containing about parts of solvent-refined turbine oil basestock, 0.04 part of a rust inhibitor comprising a reaction product oftetrapropenyl succinic anhydride and oleic acid-triethylenetetraminereaction product, prepared after the fashion of Example 2, US. PatentNo. 2,568,876, 0.25 part of di-t-butyl paracresol as an antioxidant and0.15 part of zinc dihexyldithiophosphate as an antioxidant. Theacetylenic compounds are added to the oil composition in the amountsshown, based on such composition, as set forth in Table 1, wherein thetest results are shown.

TABLE 1 Time to 3 ml.

emul., min.

(A) Heavy turbine circulating oil composition 59 (B) A+0.1% 3-methyl1-pentyn-3-ol 51 (C) A+O.5% 3-methyl 1-pentyn-3-ol 52 (D) A+1.0%3-methyl 1-pentyn-3-ol 50 (E) A+0.1% 3-chloro-3-methyl-l-pentyne 41 (F)A+O.5% 3-chloro-3-methyl-l-pentyne 34 (G) A+1.0%3-chloro-3-methyl-l-pentyne 26 (H) A+0.1% ethynyl cyclohexanol 51 Timeto 3 ml.

' emul., min.

(I) A+0.5%'ethynyl cyclohexanol 52 (J) A+l.0% ethynyl cyclohexanol 46(K) A+O.l% 3,5-dimethyl 1-heXyn-3-ol 50 (L) A+0.5% 3,5-dimethyl1-hexyn-3-ol 47 (M) A+1.0% 3,5-dimethyl1-hexyn-3-ol 43 (N) A+0.l%3-phenyl 1-butyn-3-o1 51 (O) A+0.5% '3-phenyl 1-butyn-3-ol 49 (P) All.0%3-pheny11-butyn-3-ol 38 EXAMPLE 2 A second series of tests were carriedout as in Example 1, using a somewhat lighter oil blend containing about100 parts of a lubricating oil base stock, 0.2 part zinedihexyldithiophosphate as an antioxidant and 0.1 part of the sameanti-rust agent used in Example 1, viz., the reaction product oftetrapropenyl succinic anhydride with the reaction product oftriethylenetetramine and oleic acid. The results of these tests areshown in Table 2.

TABLE 2 Time to 3 ml. emul., min. (A) Lubricating oil blend 42 (B)A+1.0% S-methyl 1-pentyn-3-ol 36 (C) A+2.0% 3-methyl 1-pentyn-3-ol 36(D) A+4.0% 3-methyl 1-pentyn-3-ol 35 (E) A+1.0% 3-methyl 1-nonyn-3-ol 25(F) A+2.0% B-methyl 1-nonyn-3-ol 17 (G) A+4.0% 3-methyl 1-nonyn-3-ol 16(H) A+1.0% 3,5-di-methyl 1-hexyn-3-ol 28 (I) A+2.0% 3,5-dimethyl1-hexyn-3-ol 27 (J) A+4.0% 3,5-dimethyl l-hexyn-3-ol 24 (K) A+1.0%ethynyl cyclohexanol 24 (L) A+2.0% ethynyl cyclohexanol 25 (M) A+4.0%ethynylcyclohexanol 22 (N) A+l.0% 3-phenyl l-butyn-3-ol 27 (O) A+2.0%3-phenyl1-butyn-3-ol 26 (P) A+0.5% 4-ethyl l-octyn-3-ol 32 (Q) A+1.0%4-ethyl 1-octyn-3-ol 32 (R) A+1.5% 4-ethyl 1-octyn-3-ol 27 (S) A+2.0%4-ethyl 1-octyn-3-ol 27 (T) A+0.2% 3,6-dirnethyl-4-octyn-3,6-diol 35 (U)A+0.3% 3,6-dimethyl-4-octyn-3,6-diol 27 It will be seen from Tables 1and 2 that the acetylenic compounds of the invention are eflectivede-emulsifiers.

It will be understood that other acetylenic compounds The use of theacetylenic demulsifiers is highly advantageous since it permits thecompounding of oils with many desirable additives that otherwise wouldrender the oil blends emulsive. The invention is, therefore, not limitedto the use of the acetylenic compounds with the specific additives shownin the tests. The amount of acetylenic compound may vary Widely, rangingfrom about 0.1 to 10% of the weight of the oil blend or composition towhich the compound is added. The range is preferably between about0.1-5.0%. Higher amounts than about 10.0% are effective but may not besufiiciently economical to justify their use.

The present invention is applicable to the various lubrieating oilcompositions in which a base oil is blended with different detergents,corrosion inhibitors, antioxidants and the like. These oil compositions,chiefly because of these additives, tend to emulsify readily with waterand the emulsions formed are difficult to break down so that oil can beseparated from the water. The inclusion of relatively small amounts ofone or more of the acetylenic compounds in the oil compositions tends toprevent emulsification altogether or to rapidly demulsify such emulsionsas may be formed.

Having now fully described the invention, what is claimed as new andpatentable is:

1. A lubricating oil composition comprising a major proportion of alubricating oil and a minor proportion, from about 0.1% to about 10% byweight, of an acetylenic compound selected from the group consisting of3- methyl-1-nonyn-3-ol, 3-phenyl-1-butyn-3-ol, and 3-chloro- 3-methyl-1-pe'ntyne.

2. The composition of claim 1, wherein the acetylenic compound is3methyl-1-nonyn-3-ol.

3. The composition of claim 1, wherein the acetylenic compound is3-phenyl-1-butyn-3-ol.

4. The composition of claim 1, wherein the acetylenic compound is3-chloro-3-methyl-l-pentyne.

References Cited by the Examiner UNITED STATES PATENTS 2,493,213 l/1950Altarnura 252-35 2,997,447 8/1961 Russell 252-358 X 3,095,381 6/1963Tinnon 252-33l X DANIEL E. WYMAN, Primary Examiner. C. O. THOMAS, W. H.CANNON, Assistant Examiners.

1. A LUBRICATING OIL COMPOSITION COMPRISING A MAJOR PROPORTION OF ALUBRICATING OIL AND A MINOR PROPORTION, FROM ABOUT 0.1% TO ABOUT 10% BYWEIGHT, OF AN ACETYLENIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF3METHYL-1-NONYN-3-OL, 3-PHENYL-1-BUTYN-3-OIL, AND3-CHLORO3-METHYL-1-PENTYNE.